Science of Synthesis

Science of Synthesis is the authoritative and comprehensive reference work for the entire field of organic and organometallic synthesis.

Science of Synthesis presents the important synthetic methods for all classes of compounds and includes:

Methods critically evaluated by leading scientists

Background information and detailed experimental procedures

Schemes and tables which illustrate the reaction scope

Preface

As our understanding of the natural world increases, we begin to understand complex phenomena at molecular levels. This level of understanding allows for the design of molecular entities for functions ranging from material science to biology. Such design requires synthesis and, as the structures increase in complexity as a necessity for specificity, puts increasing demands on the level of sophistication of the synthetic methods. Such needs stimulate the improvement of existing methods and, more importantly, the development of new methods. As scientists confront the synthetic problems posed by the molecular targets, they require access to a source of reliable synthetic information. Thus, the need for a new, comprehensive, and critical treatment of synthetic chemistry has become apparent. To meet this challenge, an entirely new edition of the esteemed reference work Houben–Weyl Methods of Organic Chemistry will be published starting in the year 2000.

To reflect the new broader need and focus, this new edition has a new title, Science of Synthesis, Houben–Weyl Methods of Molecular Transformations. Science of Synthesis will benefit from more than 90 years of experience and will continue the tradition of excellence in publishing synthetic chemistry reference works. Science of Synthesis will be a balanced and critical reference work produced by the collaborative efforts of chemists, from both industry and academia, selected by the editorial board. All published results from journals, books, and patent literature from the early 1800s until the year of publication will be considered by our authors, who are among the leading experts in their field. The 48 volumes of Science of Synthesis will provide chemists with the most reliable methods to solve their synthesis problems. Science of Synthesis will be updated periodically and will become a prime source of information for chemists in the 21st century.

Science of Synthesis will be organized in a logical hierarchical system based on the target molecule to be synthesized. The critical coverage of methods will be supported by information intended to help the user choose the most suitable method for their application, thus providing a strong foundation from which to develop a successful synthetic route. Within each category of product, illuminating background information such as history, nomenclature, structure, stability, reactivity, properties, safety, and environmental aspects will be discussed along with a detailed selection of reliable methods. Each method and variation will be accompanied by reaction schemes, tables of examples, experimental procedures, and a background discussion of the scope and limitations of the reaction described.

The policy of the editorial board is to make Science of Synthesis the ultimate tool for the synthetic chemist in the 21st century.

We would like to thank all of our authors for submitting contributions of such outstanding quality, and also for the dedication and commitment they have shown throughout the entire editorial process.

The Editorial Board

October 2000

D. Bellus (Basel, Switzerland)

E. N. Jacobsen (Cambridge, USA)

S. V. Ley (Cambridge, UK)

R. Noyori (Nagoya, Japan)

M. Regitz (Kaiserslautern, Germany)

P. J. Reider (New Jersey, USA)

E. Schaumann (Clausthal-Zellerfeld, Germany)

I. Shinkai (Tsukuba, Japan)

E. J. Thomas (Manchester, UK)

B. M. Trost (Stanford, USA)

Volume Editor’s Preface

This volume of Science of Synthesis, dealing with the various approaches to alkenes, is meant to aid researchers around the world who are engaged in developing synthetic approaches to new chemical entities or improving existing routes to known compounds of any importance. The carbon—carbon double bond with which every alkene is endowed, be it a hydrocarbon or not, is one of the most versatile functional groups in an organic molecule. Considering the multitude of other functionalities with which most methods for the synthesis of alkenes are compatible, alkenes gain even more importance in organic synthesis. The classical methods of alkene preparation comprise mainly elimination reactions of various kinds. However, the development of alkene syntheses, even of the eliminations, has never stopped. On top of these developments, the classical approaches have been supplemented with new elimination methods, and the arsenal of tools has been broadened particularly by the various carbonyl alkenation methodologies, the multitude of metal-catalyzed and metal-mediated cross couplings, including the Mizoroki--Heck reaction, as well as the modern ways of converting simple alkenes into more complex ones by the so-called metathesis principle. The development of these latter methods especially is continuing at a rapid rate, creating new improvements with wider applicability every year. Thus, this volume on alkenes covers the whole spectrum of alkene syntheses, and their applications, that have been discovered in more than 130 years.

As the volume editor I have enjoyed once again collaborating with a highly competent team of scientific editors, copy editors, artwork producers, and others at Thieme, directed by the managing editor Dr. M. Fiona Shortt de Hernandez. Their professionalism and impressively great care in their permanent engagement has brought forward a quality product that is virtually unequalled. It goes without saying that all of this would not have been achieved without the tremendous efforts of all of the authors who have contributed to this volume. Finally, I would like to thank Prof. Dr. Eric N. Jacobsen, the responsible member of the Editorial Board, and Dr. Joe P. Richmond, the independent advisor for Science of Synthesis, for their invaluable help at the beginning of this endeavour, especially in organizing the table of contents and putting together a list of competent authors.

Volume Editor

Göttingen, October 2009

Armin de Meijere

Volume 47a: Alkenes

Preface

Volume Editor’s Preface

Table of Contents

Introduction

A. de Meijere

47.1 Product Class 1: Alkenes

47.1.1 Synthesis by Alkenation Reactions

47.1.1.1 Wittig and Related Phosphorus-Based Alkenations

R. Schobert, C. Hölzel, and B. Barnickel

47.1.1.2 Peterson Alkenation

D. J. Ager

47.1.1.3 Julia, Julia–Kocienski, and Related Sulfur-Based Alkenations

I. E. Markó and J. Pospíšil

47.1.1.4 Alkenation with Metal Carbenes and Related Reactions

N. A. Petasis

47.1.1.5 McMurry Coupling and Related Reductive Dimerization Reactions

T. Takeda and A. Tsubouchi

47.1.1.6 Alkene Metathesis

M. Michalak, Ł. Gułajski, and K. Grela

47.1.2 Synthesis by Metal-Mediated Coupling Reactions

47.1.2.1 Cross-Coupling and Heck Reactions

D. A. Alonso and C. Nájera

47.1.2.2 SN′ Allylations

M. Cherkinsky and S. Levinger

47.1.2.3 π-Allyl Substitution

G. Sartori and R. Maggi

47.1.2.4 Oligomerization of Alkenes to Higher Alkenes

M. Yus and F. Foubelo

Keyword Index

Author Index

Abbreviations

Table of Contents

Introduction

A. de Meijere

Introduction

47.1 Product Class 1: Alkenes

47.1.1 Synthesis by Alkenation Reactions

47.1.1.1 Wittig and Related Phosphorus-Based Alkenations

R. Schobert, C. Hölzel, and B. Barnickel

47.1.1.1 Wittig and Related Phosphorus-Based Alkenations

47.1.1.1.1 Monosubstituted Alkenes

47.1.1.1.1.1 Method 1: Synthesis from Aldehydes and Methylenetriphenylphosphorane

47.1.1.1.1.1.1 Variation 1: Wittig Alkenation with Methylenetriphenylphosphorane Generated In Situ

47.1.1.1.1.1.2 Variation 2: Wittig Alkenation with Methylenetriphenylphosphorane and Aldehyde Generated In Situ

47.1.1.1.1.1.3 Variation 3: Wittig Alkenation under Phase-Transfer Conditions

47.1.1.1.1.1.4 Variation 4: Synthesis of ¹³C- and ²H-Labeled Terminal Alkenes from Labeled Methyltriphenylphosphonium Halides

47.1.1.1.1.2 Method 2: Synthesis from Formaldehyde and Alkylidenetriphenylphosphoranes

47.1.1.1.2 1,1-Disubstituted Alkenes

47.1.1.1.2.1 Method 1: Synthesis from Ketones and Methylenetriphenylphosphorane

47.1.1.1.2.2 Method 2: Synthesis from Formaldehyde and Alkylidenetriphenylphosphoranes

47.1.1.1.2.2.1 Variation 1: Wittig Alkenation with Preformed Ylides and Formaldehyde in Aqueous Solution

47.1.1.1.2.2.2 Variation 2: Wittig Alkenation with Paraformaldehyde and Ylides Formed In Situ

47.1.1.1.3 Z-1,2-Disubstituted Alkenes

47.1.1.1.3.1 Method 1: Wittig Alkenation of Preformed Stable Aldehydes

47.1.1.1.3.1.1 Variation 1: Reaction under Homogeneous Conditions

47.1.1.1.3.1.2 Variation 2: Reaction with Immobilized Ylides

47.1.1.1.3.1.3 Variation 3: Reaction under Phase-Transfer Conditions

47.1.1.1.3.2 Method 2: Wittig Alkenation of Aldehydes Prepared In Situ

47.1.1.1.3.2.1 Variation 1: Alkenation of Aldehydes Prepared In Situ by Oxidation of Alcohols

47.1.1.1.3.2.2 Variation 2: Alkenation of Aldehydes Prepared In Situ by Reduction

47.1.1.1.3.2.3 Variation 3: Alkenation of Aldehydes Prepared by Oxidation of Ylides or Alkenes

47.1.1.1.3.2.4 Variation 4: Alkenation of Masked Aldehydes

47.1.1.1.3.3 Method 3: Alkenation with (Triphenylphosphoranylidene)alkanoates and -alkoxides

47.1.1.1.3.3.1 Variation 1: Ylide Generation with an Excess of Base

47.1.1.1.3.3.2 Variation 2: Alkenation with In Situ Silylated Alkoxide Ylides

47.1.1.1.3.4 Method 4: Z-Selective Wittig–Horner Alkenation

47.1.1.1.4 E -1,2-Disubstituted Alkenes

47.1.1.1.4.1 Method 1: The Schlosser Modification of the Wittig Alkenation

47.1.1.1.4.2 Method 2: E-Selective Wittig–Horner Alkenation

47.1.1.1.4.3 Method 3: E-Selective Alkenation with Ylides Bearing Substitutents Other Than Triphenylphosphine

47.1.1.1.5 Tri- and Tetrasubstituted Alkenes

47.1.1.1.5.1 Method 1: Non-Stereocontrolled Wittig Alkenations

47.1.1.1.5.1.1 Variation 1: Synthesis with Symmetrical Phosphoranes or Ketones

47.1.1.1.5.1.2 Variation 2: Synthesis with (Cycloalkylidene)triphenylphosphoranes

47.1.1.1.5.1.3 Variation 3: Synthesis with Unsymmetrical Phosphorus Ylides and Unsymmetrical Ketones

47.1.1.1.5.2 Method 2: Stereocontrolled Alkenations

47.1.1.1.5.2.1 Variation 1: The SCOOPY Procedure

47.1.1.1.5.2.2 Variation 2: With Phosphole-Derived Ylides

47.1.1.1.5.2.3 Variation 3: Horner–Emmons and Wittig–Horner Alkenations with Phosphonates and Phosphine Oxides

47.1.1.1.5.2.4 Variation 4: Indirect Routes Based upon Stork–Zhao and Still–Gennari Modifications

47.1.1.1.6 Cycloalkenes

47.1.1.1.6.1 Method 1: Synthesis by Reaction of ω-Carbonyl-Substituted Phosphonium Salts

47.1.1.1.6.2 Method 2: Synthesis by Reaction of Vinylphosphonium Salts and ω-Carbonylated Enolates

47.1.1.1.6.3 Method 3: Synthesis by Partial Oxidation of Bis(alkylidenetriphenylphosphoranes)

47.1.1.1.6.4 Method 4: Synthesis by Reaction of Bis(alkylidenetriphenylphosphoranes) with Bisaldehydes

47.1.1.2 Peterson Alkenation

D. J. Ager

47.1.1.2 Peterson Alkenation

47.1.1.2.1 Alkenation by Addition of α-Silyl Carbanions to Carbonyl Compounds

47.1.1.2.1.1 Method 1: Generation of α-Silyl Carbanions by Direct Deprotonation of Silanes

47.1.1.2.1.2 Method 2: Generation of α-Silyl Carbanions from (Halomethyl)silanes

47.1.1.2.1.2.1 Variation 1: Halogen–Lithium Exchange

47.1.1.2.1.2.2 Variation 2: Formation of a Grignard Reagent

47.1.1.2.1.2.3 Variation 3: Formation of an Organocerium Compound

47.1.1.2.1.2.4 Variation 4: Formation of an Organosamarium Compound

47.1.1.2.1.3 Method 3: Generation of α-Silyl Carbanions by Transmetalation

47.1.1.2.1.3.1 Variation 1: Displacement of a Phenylsulfanyl Group with a Lithium Naphthalenide Species

47.1.1.2.1.3.2 Variation 2: Displacement of an Organoselanyl Group

47.1.1.2.1.3.3 Variation 3: Displacement of a Trialkylstannyl Group

47.1.1.2.1.3.4 Variation 4: Displacement of a Trialkylsilyl Group

47.1.1.2.1.4 Method 4: Generation of α-Silyl Carbanions by Addition of Alkyllithium Species to Vinylsilanes

47.1.1.2.2 Alkenation by Reduction of α-Silyl Carbonyl Compounds

47.1.1.2.2.1 Method 1: Addition of Metal Hydride Reagents

47.1.1.2.2.2 Method 2: Addition of Organometallic Reagents

47.1.1.2.2.2.1 Variation 1: Addition to α-Silyl Aldehydes

47.1.1.2.2.2.2 Variation 2: Addition to α-Silyl Ketones

47.1.1.2.2.2.3 Variation 3: Addition to α-Silyl Esters

47.1.1.2.3 Alkenation Based on Epoxide Ring Opening

47.1.1.2.3.1 Method 1: Addition of Silylmetal Species to Epoxides

47.1.1.2.3.2 Method 2: Addition to Silylated Epoxides

47.1.1.3 Julia, Julia–Kocienski, and Related Sulfur-Based Alkenations

I. E. Markó and J. Pospíšil

47.1.1.3 Julia, Julia–Kocienski, and Related Sulfur-Based Alkenations

47.1.1.3.1 Julia Alkenation

47.1.1.3.1.1 Coupling Reaction

47.1.1.3.1.1.1 Method 1: Reaction of α-Sulfonyl Anions with Aldehydes and Ketones

47.1.1.3.1.1.1.1 Variation 1: Route toward Terminal Alkenes

47.1.1.3.1.1.1.2 Variation 2: Route toward 1,2-Disubstituted Alkenes

47.1.1.3.1.1.1.3 Variation 3: Route toward Trisubstituted Alkenes

47.1.1.3.1.1.1.4 Variation 4: Route toward Tetrasubstituted Alkenes

47.1.1.3.1.1.1.5 Variation 5: Special Cases

47.1.1.3.1.1.2 Method 2: Reaction of α-Sulfonyl Anions with Esters

47.1.1.3.1.1.3 Method 3: Reaction of α-Sulfonyl Anions with α-Haloorganometal Electrophiles

47.1.1.3.1.1.4 Method 4: Reaction of α-Sulfoxide Anions with Aldehydes and Ketones

47.1.1.3.1.1.5 Method 5: Reaction of Bis-sulfones with Aldehydes and Ketones

47.1.1.3.1.1.6 Method 6: Reaction of Sulfoximides with Aldehydes and Ketones

47.1.1.3.1.2 Reductive Elimination

47.1.1.3.1.2.1 Method 1: Reaction of β-Hydroxy Sulfones

47.1.1.3.1.2.2 Method 2: Reaction of Sulfones Bearing a β-Leaving Group

47.1.1.3.1.2.2.1 Variation 1: By Cleavage of the C—S Bond Followed by the C—O Bond

47.1.1.3.1.2.2.2 Variation 2: By Cleavage of the C—O Bond Followed by the C—S Bond

47.1.1.3.1.2.3 Method 3: Reaction of β-Mesyloxy and β-Acetoxy Sulfoxides

47.1.1.3.1.2.4 Method 4: Reaction of β-Benzoyloxy Sulfoxides

47.1.1.3.1.2.5 Method 5: Reaction of β-Hydroxy Sulfoximides

47.1.1.3.2 Julia–Kocienski and S.Julia Alkenation

47.1.1.3.2.1 Method 1: Addition to Carbonyl Compounds

47.1.1.3.2.1.1 Variation 1: 1,2-Disubstituted Alkenes

47.1.1.3.2.1.2 Variation 2: Trisubstituted Alkenes

47.1.1.3.2.2 Method 2: Addition to Lactones

47.1.1.4 Alkenation with Metal Carbenes and Related Reactions

N. A. Petasis

47.1.1.4 Alkenation with Metal Carbenes and Related Reactions

47.1.1.4.1 Method 1: Synthesis by Methylenation with (μ-Chloro)bis-(η⁵-cyclopentadienyl)(dimethylaluminum)-(μ-methylene)titanium (The Tebbe Reagent)

47.1.1.4.1.1 Variation 1: Methylenation of Aldehydes

47.1.1.4.1.2 Variation 2: Methylenation of Ketones

47.1.1.4.1.3 Variation 3: Methylenation of Esters

47.1.1.4.1.4 Variation 4: Methylenation of Lactones

47.1.1.4.1.5 Variation 5: Methylenation of Miscellaneous Carbonyl Compounds

47.1.1.4.2 Method 2: Synthesis by Methylenation with Titanacyclobutanes

47.1.1.4.3 Method 3: Synthesis by Methylenation with Bis(η⁵-cyclopentadienyl)-dimethyltitanium(IV) (The Petasis Reagent)

47.1.1.4.3.1 Variation 1: Methylenation of Aldehydes

47.1.1.4.3.2 Variation 2: Methylenation of Ketones

47.1.1.4.3.3 Variation 3: Methylenation of Esters

47.1.1.4.3.4 Variation 4: Methylenation of Lactones

47.1.1.4.3.5 Variation 5: Methylenation of 1,3-Dioxolan-4-ones and 1,3-Dioxan-4-ones

47.1.1.4.3.6 Variation 6: Methylenation of Carbonates

47.1.1.4.3.7 Variation 7: Methylenation of Amides and Lactams

47.1.1.4.3.8 Variation 8: Methylenation of Miscellaneous Carbonyl Compounds

47.1.1.4.4 Method 4: Synthesis by Methylenation with gem-Dimetallic Reagents

47.1.1.4.4.1 Variation 1: Methylenation with the Nysted Reagent

47.1.1.4.4.2 Variation 2: Methylenation with Dibromomethane–Zinc–Titanium(IV) Chloride Reagents

47.1.1.4.4.3 Variation 3: Methylenation with Diiodomethane–Zinc Reagents

47.1.1.4.4.4 Variation 4: Methylenation with Dihalomethane–Magnesium Reagents

47.1.1.4.5 Method 5: Synthesis by Methylenation with Molybdenum and Tungsten Carbenes

47.1.1.4.6 Method 6: Synthesis by Methylenation with Diazo Compounds under Metal Catalysis

47.1.1.4.7 Method 7: Synthesis by Alkylidenation with Dialkylbis-(η⁵-cyclopentadienyl)titanium(IV) Reagents (Petasis Alkenation)

47.1.1.4.7.1 Variation 1: Using Dibenzylbis(η⁵-cyclopentadienyl)titanium(IV) Reagents

47.1.1.4.7.2 Variation 2: Using Bis(η⁵-cyclopentadienyl)dicyclopropyltitanium(IV)

47.1.1.4.7.3 Variation 3: Using η⁵-Cyclopentadienyl[(trimethylsilyl)methyl]-titanium(IV) Reagents

47.1.1.4.8 Method 8: Synthesis by Alkylidenation with Low-Valent Titanium Reagents (Takeda Alkenation)

47.1.1.4.8.1 Variation 1: Using Alkyl Halides

47.1.1.4.8.2 Variation 2: Using gem-Dihalides

47.1.1.4.8.3 Variation 3: Using Dithioacetals

47.1.1.4.8.4 Variation 4: Intramolecular Carbonyl Alkylidenation

47.1.1.4.9 Method 9: Synthesis by Alkylidenation with gem-Dimetallic Reagents

47.1.1.4.10 Method 10: Synthesis by Halomethylenation

47.1.1.4.10.1 Variation 1: Using Chromium Reagents (Takai Alkenation)

47.1.1.4.10.2 Variation 2: Using Titanium Reagents

47.1.1.4.11 Method 11: Synthesis by Allenation with Titanium Carbenes

47.1.1.4.11.1 Variation 1: Using Titanacyclobutanes

47.1.1.4.11.2 Variation 2: Using Alkenylbis(η⁵-cyclopentadienyl)titanium(IV) Reagents

47.1.1.4.11.3 Variation 3: Using 1,1-Dichloroalkenes

47.1.1.5 McMurry Coupling and Related Reductive Dimerization Reactions

T. Takeda and A. Tsubouchi

47.1.1.5 McMurry Coupling and Related Reductive Dimerization Reactions

47.1.1.5.1 Method 1: Self-Coupling Reactions

47.1.1.5.1.1 Variation 1: Of Aldehydes

47.1.1.5.1.2 Variation 2: Of Ketones

47.1.1.5.2 Method 2: Mixed Coupling Reactions

47.1.1.5.2.1 Variation 1: Of Aldehydes

47.1.1.5.2.2 Variation 2: Of Ketones

47.1.1.5.2.3 Variation 3: Of Aldehydes and Ketones

47.1.1.5.2.4 Variation 4: Sequential Cyclization Reactions of Dicarbonyl Compounds

47.1.1.5.3 Method 3: Intramolecular Coupling Reactions

47.1.1.5.3.1 Variation 1: Cyclization of Aliphatic Dialdehydes, Diketones, and Oxoaldehydes

47.1.1.5.3.2 Variation 2: Synthesis of [2.n]Cyclophan-1-enes by Cyclization of Two Aromatic Carbonyl Moieties Tethered by an Aliphatic Chain

47.1.1.5.3.3 Variation 3: Synthesis of [2.n]Cyclophan-1-enes by Cyclization of Bis(aromatic aldehydes and ketones) with Tethers Containing Aromatic Rings

47.1.1.5.3.4 Variation 4: Synthesis of Ethene-1,2-diyl-Bridged Calix[4]arenes by Intramolecular Cyclization of Formyl-Substituted Calixarenes

47.1.1.5.3.5 Variation 5: Synthesis of Cyclic Phenylenevinylenes and Related Polyaromatics by Intramolecular Coupling of Conjugated Diformyl Compounds Linked with Phenylene and/or Vinylene Moieties

47.1.1.5.3.6 Variation 6: Synthesis of Tetrapyrrolic Macrocycles by Intramolecular Coupling of Formyl Groups at the Ends of Acyclic Tetrapyrroles

47.1.1.5.3.7 Variation 7: Synthesis of Ferrocenophanes by Intramolecular Coupling of Ferrocene-Derived Bis(aldehydes)

47.1.1.5.3.8 Variation 8: Synthesis of Condensed Polyaromatics by Intramolecular Coupling of 2,2′-Diformylbiaryls and Related Compounds

47.1.1.5.3.9 Variation 9: Synthesis of Heterocycles by Intramolecular Cyclization of Bis(aldehydes) and Bis(ketones) with a Heteroatom-Containing Tether

47.1.1.5.3.10 Variation 10: Synthesis of Annulenes by Intramolecular Coupling of Conjugated Polyene Dialdehydes and Ketones

47.1.1.5.3.11 Variation 11: Miscellaneous Reactions

47.1.1.5.4 Method 4: Coupling in Polymer Synthesis

47.1.1.6 Alkene Metathesis

M. Michalak, Ł. Gułajski, and K. Grela

47.1.1.6 Alkene Metathesis

47.1.1.6.1 Method 1: Cross Metathesis of a Reactive Alkene

47.1.1.6.1.1 Variation 1: Reaction with a Fast Homodimerizing Metathesis Partner

47.1.1.6.1.2 Variation 2: Reaction with a Very Slow Homodimerizing Metathesis Partner

47.1.1.6.1.3 Variation 3: Reaction with a Very Slow Homodimerizing Metathesis Partner or a Spectator

47.1.1.6.2 Method 2: Ring-Closing Metathesis

47.1.1.6.2.1 Variation 1: Synthesis of Cycloalkenes with Disubstituted Double Bonds

47.1.1.6.2.2 Variation 2: Synthesis of Cycloalkenes with Trisubstituted Double Bonds

47.1.1.6.2.3 Variation 3: Synthesis of Cycloalkenes with Tetrasubstituted Double Bonds

47.1.1.6.3 Method 3: Ene–Yne Metathesis

47.1.1.6.3.1 Variation 1: Cross Ene–Yne Metathesis

47.1.1.6.3.2 Variation 2: Ring-Closing Ene–Yne Metathesis

47.1.1.6.4 Method 4: Acyclic Diene Metathesis Polymerization

47.1.1.6.5 Method 5: Ring-Opening Metathesis

47.1.1.6.5.1 Variation 1: Ethenolysis

47.1.1.6.5.2 Variation 2: Ring-Opening with Concomitant Cross Metathesis

47.1.1.6.5.3 Variation 3: Ring-Opening with Concomitant Ring-Closing Metathesis

47.1.1.6.6 Method 6: Ring-Opening Metathesis Polymerization

47.1.2 Synthesis by Metal-Mediated Coupling Reactions

47.1.2.1 Cross-Coupling and Heck Reactions

D. A. Alonso and C. Nájera

47.1.2.1 Cross-Coupling and Heck Reactions

47.1.2.1.1 Palladium-Catalyzed C—C Coupling Reactions

47.1.2.1.1.1 Method 1: Synthesis by the Mizoroki–Heck Reaction

47.1.2.1.1.2 Method 2: Synthesis by Suzuki–Miyaura Coupling

47.1.2.1.1.2.1 Variation 1: Reaction of B-Alkenyl Compounds with Alkyl Electrophiles

47.1.2.1.1.2.2 Variation 2: Reaction of B-Alkyl Compounds with Alkenyl Electrophiles

47.1.2.1.1.3 Method 3: Synthesis by Kosugi–Migita–Stille Coupling

47.1.2.1.1.3.1 Variation 1: Reaction of Alkenylstannanes with Alkyl Electrophiles

47.1.2.1.1.3.2 Variation 2: Reaction of Alkylstannanes with Alkenyl Electrophiles

47.1.2.1.1.4 Method 4: Synthesis by Corriu–Kumada–Tamao Coupling

47.1.2.1.1.4.1 Variation 1: Reaction of Alkyl Grignard Compounds with Alk-1-enyl Halides

47.1.2.1.1.4.2 Variation 2: Reaction of Grignard Reagents with Allyl Electrophiles

47.1.2.1.1.5 Method 5: Synthesis by Negishi Coupling

47.1.2.1.1.5.1 Variation 1: Reaction of Alkylzinc Compounds with Alkenyl Electrophiles

47.1.2.1.1.5.2 Variation 2: Reaction of Alkenylzinc Reagents with Alkyl Electrophiles

47.1.2.1.1.5.3 Variation 3: Reaction of Alkenylzirconium Compounds with Alkyl Electrophiles

47.1.2.1.1.5.4 Variation 4: Reaction of Alkenylaluminum Compounds with Alkyl Electrophiles

47.1.2.1.1.6 Method 6: Synthesis by Organoindium Cross-Coupling Reactions

47.1.2.1.2 Nickel-Catalyzed C—C Coupling Reactions

47.1.2.1.2.1 Method 1: Synthesis by Suzuki–Miyaura Coupling

47.1.2.1.2.2 Method 2: Synthesis by Negishi Coupling

47.1.2.1.2.3 Method 3: Synthesis by Corriu–Kumada–Tamao Coupling

47.1.2.1.2.3.1 Variation 1: Reaction of Alkyl Grignard Reagents with Alkenyl Electrophiles

47.1.2.1.2.3.2 Variation 2: Reaction of Grignard Reagents with Dithioacetals

47.1.2.1.3 Iron-Catalyzed C—C Coupling Reactions

47.1.2.1.3.1 Method 1: Synthesis by Desulfinylative Mizoroki–Heck-Type Reaction

47.1.2.1.3.1.1 Variation 1: Reaction of Alkenyl Grignard Reagents with Alkanesulfonyl Chlorides

47.1.2.1.3.2 Method 2: Synthesis by Corriu–Kumada–Tamao Coupling

47.1.2.1.3.2.1 Variation 1: Reaction of Alkyl Grignard Reagents with Alkenyl Electrophiles

47.1.2.1.3.2.2 Variation 2: Reaction of Alkenyl Grignard Compounds with Alkyl Electrophiles

47.1.2.1.3.2.3 Variation 3: Reaction of Grignard Reagents with Allyl Electrophiles

47.1.2.1.4 Cobalt-Catalyzed C—C Coupling Reactions

47.1.2.1.4.1 Method 1: Synthesis by Corriu–Kumada–Tamao Coupling

47.1.2.1.4.1.1 Variation 1: Reaction of Alkyl Grignard Reagents with Alkenyl Electrophiles

47.1.2.1.4.1.2 Variation 2: Reaction of Allyl Grignard Reagents with Alkyl Electrophiles

47.1.2.1.4.2 Method 2: Synthesis by Negishi Coupling

47.1.2.1.4.2.1 Variation 1: Coupling of Alkylzinc Compounds with Alkenyl Electrophiles

47.1.2.1.4.2.2 Variation 2: Coupling of Alkylzinc Compounds with Allyl Electrophiles

47.1.2.1.4.2.3 Variation 3: Reaction of Arylzinc Compounds with Allyl Electrophiles

47.1.2.2 SN′ Allylations

M. Cherkinsky and S. Levinger

47.1.2.2 SN′ Allylations

47.1.2.2.1 Method 1: Synthesis of Alkenes Using Grignard Reagents

47.1.2.2.1.1 Variation 1: Catalyzed Reactions with Achiral Catalysts

47.1.2.2.1.2 Variation 2: Catalyzed Reactions with Chiral Catalysts

47.1.2.2.2 Method 2: Synthesis of Alkenes Using Organocopper Reagents

47.1.2.2.3 Method 3: Synthesis of Alkenes Using Lithium Organocuprate Reagents

47.1.2.2.3.1 Variation 1: Using Lower-Order Lithium Organocuprate Reagents

47.1.2.2.3.2 Variation 2: Using Lithium Heteroorganocuprate Reagents

47.1.2.2.3.3 Variation 3: Using Higher-Order Lithium Organocuprate Reagents

47.1.2.2.4 Method 4: Synthesis of Alkenes Using Organozinc Reagents

47.1.2.2.4.1 Variation 1: Using Zinc Organocuprate Reagents

47.1.2.2.4.2 Variation 2: Using Diorganozinc Reagents

47.1.2.2.5 Method 5: Synthesis of Alkenes Using Organoaluminum Reagents

47.1.2.3 π-Allyl Substitution

G. Sartori and R. Maggi

47.1.2.3 π-Allyl Substitution

47.1.2.3.1 Palladium-Catalyzed Reactions

47.1.2.3.1.1 Method 1: Synthesis of Alkenes Using Carbon Nucleophiles

47.1.2.3.1.1.1 Variation 1: Using Nonstabilized or Stabilized Enolates

47.1.2.3.1.1.2 Variation 2: Using Miscellaneous Nucleophiles

47.1.2.3.1.2 Method 2: Synthesis of Alkenes Using Nitrogen, Oxygen, or Sulfur Nucleophiles

47.1.2.3.2 Other Metal-Catalyzed Reactions

47.1.2.3.2.1 Method 1: Synthesis of Alkenes Using Iron Catalysts

47.1.2.3.2.2 Method 2: Synthesis of Alkenes Using Ruthenium Catalysts

47.1.2.3.2.3 Method 3: Synthesis of Alkenes Using Miscellaneous Metal Catalysts

47.1.2.4 Oligomerization of Alkenes to Higher Alkenes

M. Yus and F. Foubelo

47.1.2.4 Oligomerization of Alkenes to Higher Alkenes

47.1.2.4.1 Method 1: Oligomerization of Ethene

47.1.2.4.1.1 Variation 1: Using Metallocenes and Related Complexes

47.1.2.4.1.2 Variation 2: Using Tridentate Bis(imino)pyridine Complexes of Transition Metals

47.1.2.4.1.3 Variation 3: Using SHOP-Type and Related Complexes

47.1.2.4.2 Method 2: Oligomerization of Propene

47.1.2.4.3 Method 3: Oligomerization of Higher Alk-1-enes

Keyword Index

Author Index

Abbreviations

Introduction

A. de Meijere

Alkenes are endowed with a C=C bond, and this constitutes the simplest, yet one of the most versatile, functional groups in organic molecules. In terms of worldwide annual production by the petrochemical industry, the simple alkenes, namely ethene, propene, and the isomeric butenes, play the dominant role, and are building blocks for a vast number of chemical intermediates and final consumer products. In this volume of Science of Synthesis (consisting of two subvolumes, 47a and 47b), the various methods for the preparation of alkenes are discussed and evaluated. The focus is on purely hydrocarbon alkenes and cycloalkenes without any functional groups directly attached to the C=C bond; such functionalized compounds constitute other product classes that are covered in other volumes of Science of Synthesis, according to the organizational system employed in the series. However, some of the established methods that need to be covered here, at least briefly for systematic reasons, have mostly or even solely been used to prepare such functionally substituted examples, while alkenes with remote functional groups are also included here, with cross-references to other volumes of Science of Synthesis whenever necessary. Previously published reviews, book chapters, and books on any of the presented methods are referred to wherever applicable.

There is a stunningly great variety of methods to access alkenes from appropriately functionalized alkanes (see ▶ Table 1 for a schematic listing). The first sections of this volume are devoted to the various carbonyl alkenation (olefination) reactions such as the Wittig reaction and related phosphorus-based alkenations (▶ Section 47.1.1.1), the Peterson alkenation (▶ Section 47.1.1.2), and the Julia and Julia–Kocienski alkenations as well as further related sulfur-based alkenations (▶ Section 47.1.1.3), which all have some mechanistic similarities. The more recently developed alkenations of carbonyl compounds with metal carbenes such as the Tebbe and Petasis reagents, as well as with gem-dimetallic species, are also in the same group of transformations (▶ Section 47.1.1.4), and so is the so-called McMurry coupling of (preferably) two identical carbonyl compounds (▶ Section 47.1.1.5). All of these methods have found a wide range of applications in the synthetic laboratory, and some have even been employed in industrial scale production. Alkene metathesis (▶ Section 47.1.1.6), on the other hand, had been used in the petrochemical industry for the conversion of simple alkenes into higher alkenes long before this methodology became applicable to more complex organic molecules with the advent of new classes of catalysts with wide functional-group tolerances. This development was initiated mainly by Grubbs and by Schrock and their coworkers, for which these two scientists shared the Nobel Prize in 2005. Other groups have joined in and made important contributions from the 1990s onwards.

The various transition-metal-catalyzed cross couplings (▶ Section 47.1.2) including the Mizoroki–Heck reaction, the SN′ allylations of organometallic compounds, and π-allyl substitutions, all of which were discovered in the 1960s and 1970s, some initially as stoichiometric reactions, now find a wide range of applications in research laboratories, and some have made their way into the production processes for fine chemicals in industry. The metal-catalyzed oligomerization of alkenes to higher alkenes, discussed in ▶ Section 47.1.2.4, has its importance only on the industrial scale.

Table 1 Schematic View of the Synthetic Routes to Alkenes Including Cycloalkenes, and the Corresponding Section in Volume 47

Method
Representative Reaction(s)a
Section

Wittig and related phosphorus-based alkenations
missing link
47.1.1.1

Peterson alkenation
missing link
47.1.1.2

Julia, Julia–Kocienski, and related sulfur-based alkenations
missing link
47.1.1.3

alkenation with metal carbenes and related reactions
missing link
47.1.1.4

McMurry coupling and related reductive dimerization reactions
missing link
47.1.1.5

alkene metathesis
missing link
47.1.1.6

cross coupling and Heck reactions
missing link
47.1.2.1

SN′ allylation of organometallic compounds
missing link
47.1.2.2

π-allyl substitution
missing link
47.1.2.3

oligomerization of alkenes to higher alkenes
missing link
47.1.2.4

Diels–Alder reactions ([4 + 2] cycloadditions)
missing link
47.1.3.1

ene reactions
missing link
47.1.3.2

4π-electrocyclic reactions
missing link
47.1.3.3.1

Cope rearrangement
missing link
47.1.3.3.3

oxidative decarboxylation and decarbonylative elimination
missing link
47.1.4.1

oxidative decarboxylation of dicarboxylic acid derivatives
missing link
47.1.4.2

base- and otherwise catalyzed elimination from alkyl halides, methanesulfonates, toluenesulfonates, ethers, sulfides, ammonium salts, and sulfonium salts
missing link
47.1.4.3

acid-catalyzed dehydration of alcohols
missing link
47.1.4.4

pyrolytic elimination from esters, xanthates, phosphates, thiophosphates, sulfamates, amine N-oxides, ammonium hydroxides, phosphonium salts, and others
missing link
47.1.4.5

reductive elimination from β-halohydrins and their esters or ethers
missing link
47.1.4.6

reductive elimination from gem-dihalides
missing link
47.1.4.7

reductive extrusion from three-to six-membered heterocycles
missing link
47.1.4.8

reactions of (arylsulfonyl)hydrazones with strong bases (Bamford–Stevens and Shapiro reactions)
missing link
47.1.4.9

dehydrogenation of CH₂ߞCH₂ fragments
missing link
47.1.4.10

[2 + 2]-cycloaddition reactions
missing link
47.1.5.1

hydrogenation reactions (catalytic hydrogenation and chemical reduction)
missing link
47.1.5.2

elementometalations (including hydrometalation) and subsequent cross-coupling reactions
missing link
47.1.5.3

carbometalation and subsequent cross-coupling reactions
missing link
47.1.5.4

dissolving-metal (Birch-type) reduction of arenes
missing link
47.1.6.1

catalytic hydrogenation and chemical reduction of allenes
missing link
47.1.6.2

catalytic hydrogenation and chemical reduction (e.g., dissolving-metal reduction, hydrocarbonation by organometallic reagents, diimide reduction) of 1,3- and higher dienes
missing link
47.1.6.3,
47.1.6.4

isomerization of alkenes
missing link
47.1.7

synthesis from other alkenes without isomerization (electrophilic and nucleophilic substitution)
missing link
47.1.8

syntheses of cyclopropenes
missing link
47.2.1

syntheses of nonconjugated di-, tri-, and oligoenes
missing link
47.3.1

a Possible stereoisomers and/or regioisomers in products are not shown.

The classical Diels–Alder reaction, including its modern catalyzed versions, along with the so-called ene reactions and electrocyclic reactions make up Sections 47.1.3.1–47.1.3.3. Among these, the Diels–Alder reaction has by far the widest application, as it is the simplest and most atom-economical way to prepare cyclohexene derivatives of any sort. Ene reactions have only a rather limited range of applicability, but the modern “metallo-ene” reactions {see, for example, Science of Synthesis, Vol. 36 [Alcohols (Section 36.2.3.1.4.5)]} are among the most versatile methods for the elegant construction of cyclic and oligocyclic skeletons.

Of course, elimination reactions constitute the largest arsenal of methods for the preparation of alkenes (Section 47.1.4). They range from eliminations of carbonyl or carboxy groups, the latter either without or along with the elimination of a second carboxy or a hydroxy group, via base- or acid-catalyzed or pyrolytic eliminations of HX (in which X can be any leaving group), to the reductive elimination of two vicinal or geminal leaving groups. Such eliminations can proceed regioselectively and some of them are even stereoselective. In particular, the reductive extrusions of oxygen, sulfur, and sulfur dioxide from oxiranes, thiiranes, and thiirane 1,1-dioxides (including in situ formed thiirane 1,1-dioxides in the so-called Ramberg–Bäcklund reaction), respectively, occur stereoselectively. This also holds for the reductive extrusion of sulfur and carbon dioxide or sulfur and carbon disulfide from dioxolane- and dithiolane-2-thiones, respectively. The mechanistically interesting Bamford–Stevens and Shapiro reactions, which occur upon treatment of ketone (arylsulfonyl)hydrazones with 1 and 2 equivalents, respectively, of an organometallic reagent (usually butyl- or methyllithium), complement the vast range of elimination reactions. The latter have most frequently been employed for the preparation of cyclic and oligocyclic alkenes.

Alkynes in general are more precious than alkenes, and they are frequently prepared from the latter. However, they also serve as valuable starting materials for alkenes by various addition reactions (Section 47.1.5). While [2 + 2]-cycloaddition reactions to furnish cyclobutenes have a rather limited range of applications, reductions by stereospecific catalytic hydrogenation and by chemical reduction are frequently employed to transform oligofunctional alkynes, which are more easily assembled than the correspondingly substituted alkenes, into the latter target compounds. Modern transition-metal-catalyzed elementometalations [including hydrometalation (Section 47.1.5.3) and carbometalation (Section 47.1.5.4)] especially, with or without subsequent cross coupling, have gained enormous importance since the 1980s for the access to a wide range of functionalized and nonfunctionalized alkenes, as well as conjugated and nonconjugated di-, tri-, and oligoenes.

Partial reductive removal of double bonds from cumulated and conjugated dienes, trienes, and arenes can also serve as an access to simpler alkenes and cycloalkenes (Section 47.1.6). Thus, the so-called Birch reduction, i.e. the treatment of arenes with lithium metal in liquid ammonia (or the Benkeser version using lithium in a primary amine), provides convenient access to substituted cyclohexa-1,4-dienes and cyclohexenes. Catalytic hydrogenation as well as Birch-type reduction of allenes (1,2-dienes) occurs selectively at the least-substituted double bond, and 1,3-dienes formally undergo 1,4-addition of hydrogen under Birch reduction conditions; this can be performed in the presence of an additional nonconjugated double bond in the same molecule.

Isomerizations of alkenes (Section 47.1.7) are only of industrial importance, with the exception of the isomerization of vinylcyclopropanes to cyclopentenes, which has gained ever increasing attention since its discovery around 1960 as a method to access five-membered carbocycles. Certain alkenes are most easily accessible by electrophilic or nucleophilic substitutions of appropriately activated (i.e., usually functionally substituted in the case of nucleophilic substitutions) alkenes without isomerizations (Section 47.1.8.

Methods for the syntheses of cyclopropenes (Section 47.2) and of nonconjugated di-, tri-, and oligoenes (Section 47.3) are discussed in two separate sections, although most of the employed methods are basically the same as those discussed in various preceding sections.

47.1 Product Class 1: Alkenes

47.1.1 Synthesis by Alkenation Reactions

47.1.1.1 Wittig and Related Phosphorus-Based Alkenations

R. Schobert, C. Hölzel, and B. Barnickel

General Introduction

Previously published information regarding the synthesis of all-carbon substituted alkenes by means of Wittig and related phosphorus-based alkenation reactions can be found in the Houben–Weyl and Science of Synthesis sections dealing with the applications of the respective phosphorus reagents, e.g. in Houben–Weyl, Vol. 12/1, p 112 and Vol. E 1, p 616 and in Science of Synthesis, Vol. 27 [Heteroatom Analogues of Aldehydes and Ketones (Section 27.24.2.2)]. Other comprehensive monographs[1–3] on the subject are also available. The synthesis of alkenes with adjacent carbonyl or carboxy groups has been covered in the Science of Synthesis sections on α,β-unsaturated aldehydes {Vol. 25 [Aldehydes (Section 25.8.1.1.12.2)]}, enones {Vol. 26 [Ketones (Section 26.9.1.1.9)]}, and α,β-unsaturated esters {Vol. 20b [Three Carbon—Heteroatom Bonds: Esters and Lactones; Peroxy Acids and R(CO)OX Compounds; R(CO)X, X = S, Se, Te (Section 20.5.14.1.4)]}.

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